Catalytic conversion of hydrocarbons



Patented Aug. 12, 1947 CATALYTIC CONVERSION OF HYDROCARBONS Allen D. Garrison, Houston, Tex., assignor to Texaco Development Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 13, 1944,

. Serial No. 535,551

This invention relates to the catalytic conversion of hydrocarbons, and particularly to the been treated with anhydrous silicon tetrafluoridel The invention has to do with manufacturing and reactivating catalysts containing alumina.

,More specifically, the invention accomplishes (a) a rapid and economical method of manufacturing hydrocarbon conversion catalysts from relatively cheap raw materials, and (b) a new and.

convenient method for reactivation of such catalysts which have already been in use.

Hydrocarbon conversions of the character anticipated are commonly conducted at such temperatures and pressures that the hydrocarbons are in the vapor state, while the catalysts are solids. The solid catalyst may be either stationary or in motion, but in either case it is desirable for the catalyst to have an extended area in order that the catalyst may be rapidly accessible to the hydrocarbon vapors, and it is essential that the surface of the catalyst shall act to accelerate the formation of the gasoline components and favor g'the formation of compounds which have desira le properties as fuels. It is common experielice that catalysts for such hydrocarbon conve sions are more or less limited in their useful life, either by mechanical loss as is commonly encountered in the moving bed technique or by gradual deterioration of the catalytic function with repeated use and regenerations. It is therefore obviously desirable to be able to manufacture suitable catalysts at low cost and to be able to reactivate catalysts wherein the activity has been partly lost by repeated use.

The invention has application particularly to the catalytic cracking of hydrocarbons, although it is contemplated that it may have application to other catalytic conversion processes such as cracking or reforming of naphtha or gasoline hydrocarbons to produce gasoline hydrocarbons of improved characteristics such as increased antiknock value. The invention may have application to catalytic polymerization and isomerization of olefin hydrocarbons into olefins of more branched chain character In accordance with the invention aluminum oxide, preferably alumina with highly developed surface, which normally exhibits low activity and yields gasoline having undesirable properties 2 Claims. (01. 196-52) when used as a. catalyst for cracking gas oil, is treated with anhydrous silicon tetrafluoride at a temperature in the range to 950 F. for a short period of time ranging from a few seconds to a few minutes or longer, and as a result is converted into a catalyst of greatly increased activity and desirability. The alumina when in suitable form takes up or reacts witha substantial amount of silicon tetrafluoride amounting to as much as 5% to 15% by weight of the aluminum oxide.

The nature of the activating action of SiF4 is not understood. It may involve physical adsorption or chemical adsorption of silicon tetrafiuoride, or chemical reaction between the treating agent and aluminum oxide, or combinations, of these phenomena. It is essential for the catalyst to contain at least about 5% and preferably 7% by weight of silicon tetrafluoride in adsorbed or in chemical combination therewith in order to have properly increased activity and yield gasoline having good qualities.

Alumina containing compounds in which the alumina may or may not be present in gel form may be treated in accordance with this invention. Such compounds comprise activated alumina," dehydrated bauxite, Porocel, and synthetic gel compounds such as silica-alumina complexes, or silica-alumina-zirconia gels containing, for example, about parts by weight of Si02, 2 parts by weight of A1203, and 5 parts of ZrOz.

It has been proposed heretofore to treat clays and the like with aqueous solutions containing fluorine such as a solution of hydrofluosilicic acid, but such treatments produce hydrated compounds of aluminum and fluorine and involve an etching effect not characteristic of the catalyst of my invention. There are other advantages which will alumina with an aqueous solution of a fluorine compound such as hydrofiuosilicic acid.

Alumina or compositions rich in alumina,

' when precipitated from water solutions either in formation, and have structures whichconform to V the following names and formulae: boehmite, Y-AlzOa-I-IzO; gibbsite, 7-A1zO3'3I-I2O; diaspore, c-AlzOa-HzO; and bayerite, a-AI203'3H20. In natural bauxite, for example, the hydrated gamma forms of alumina, boehmite, and gibbsite, predominate. g

A relatively economical source of almost pure alumina hydrate is available in the modification of the Bayer process. Impure natural alumina is dissolved in hot caustic solution, which eliminates the iron impurities, and is reprecipitated by adding an acid, such as carbonic acid. A hard crystalline form of alumina (bayerite) separates in a scale or crust, is periodically removed with pneumatic drills, and may be crushed, screened and washed almost completely free of impurities.

Since my invention involves an essentially anhydrous reaction between alumina and dry silicon tetrafluoride, it is necessary to remove the water from the hydrated bauxite or alumina almost completely. This removal of water is essential for another reason, namely, that it disrupts the original crystals and produces a form of alumina which has a very much enlarged surface. It is an outstanding feature of my invention that this large surface may be activated and preserved by a method which is rapid and relatively economical.

Alumina having its area thus greatly extended is available on the commercial market as Activated Alumina. The activation may be executed by heating, as described in U. 8. Patents Nos. 1,868,869 and 2,015,593, and the result is a hard, porous, adsorbent material consisting large- 1y of a form of gamma alumina" which is not hydrated and some ,alpha-monohydrate alumina. Maximum adsorption and maximum area of the solid appear when the water content of the solid has been reduced to about 7% by controlled heating. This is not free water in any sense, but remains combined either as a part of the structure of some of the crystals or as water which is very tenaciously adsorbed (chemsorD- tion) on the most active surface areas. An example of such an activated alumina and one useful in the operation of my invention is a material called Alorco-A which contains about 92% of A1203, 7% firmly bound water, less than 1% sodium oxide from the caustic which was not completely-removed in the washing process and very small traces of silica, iron oxides and titania. The sodium oxide content can be further reduced by washing with very dilute acids or by electrodialysis. l

The term bauxite is used universally to identify rocks containing certain forms of hydrated alumina as their major constituent. The three recognized forms of alumina are: diaspore or alpha-alumina-monohydrate; boehmite or gamma-alumina-monohydrate; and gibbsite or gamma-alumina-trihydrate, These hydrated materials have relatively large crystals, are not good adsorbents and do not have extended surface areas. They may contain from 12% to 30%,of water. In their original state they are thus not suitable for the preparation of the active catalysts by interaction with dry SiF4.

bauxites may be converted into activated bauxites by heating to temperatures in the range 600 F. to 900 R, where almost all of the water is driven 013. and where the dehydrated alumina However, I

develops a large surface area (as much as 290 Q square meters per gram) and where the adsorp-' tive capacity may attain a maximum. As in the case of the artificial activated alumina, the maximum area appears when the water has been reduced to as low as 7% and where the remaining water is extremely firmly bound. An example of an activated alumina prepared from bauxite is a material called Porocel which is subject These dehydrated aluminas may have surfacev areas which are large and other physical properties which adapt them to catalytic functions, but

, their surface character is such that they do not v oxide,-flue gas, nitrogen, and various hydrocar-v satisfactorily accelerate the formation of gasoline hydrocarbons, and such hydrocarbons as are formed do not have high value as fuels. My invention provides a rapid, economical and eflicient mode of activating the dehydrated alumina so that the desirable physical properties of the a1u-.

compounds in solution, since adsorbed air or other gases prevent the complete distribution of the liquid agent into the alumina: grains, andsince diffusion is very retarded in the liquid state. Furthermore, it is advantageous to retain the hard granular form of the alumina, to avoid etching .or weakening of its physical structure, and to preserve the highly developed area which is characteristic of good adsorptive dehydrated alumina. In these respects the invention herein described is a distinct improvement over methods of activation heretofore disclosed.

I have discovered that the speed of the activation reaction is limited only by the time required for the silicon tetrafluoride gas to enter the structure of the alumina and contact the inner surfaces. Any convenient means of accomplishing this is satisfactory. The gas may be simply passed through a bed of the dehydrated alumina granules, or the alumina in granular or powder form may be dropped or otherwise passed through the silicon tetrafiuoride gas. I have determined that the presence of other gases which'are inert t the fluoride are not detrimental. Dry air, carbon dibon vapors may be used to dilute the fluoride gas without ill effects. The composition of such mixed gases may vary from a few per cent SiF4 to The optimum amount of silicon tetrafiuor'ide may sel.

A characteristic property of dehydrated alumina is its great aftinity forwater.

This gas be admitted to the alumina in an evacuated ves- The water becomes attached to the alumina by surface adsorption and the solid structure remains practically intact, there being no tendency to return to the original hydrated aluminas which were present prior to the thermal dehydration. Be-

cause of this great afilnity for water, it is difflcult to handle samples without some slight contact with moist gas and therefore some slight contamination with adsorbed water. I have found, however, that this slight additional adsorbed water is not decidedly harmful in the practice of my invention, although it is better to avoid it. A slight additional amount of silicon tetrafluoride is required to accomplish the activation if such adsorbed water is present, and the activity of the activated catalyst is slightly reduced. For example, the activation of a sample of Alorco-A which has been handled without extreme precautions to avoid a little contamination with water vapor required at least 8.8%

SiF4 by weight of alumina to develop optimum artivity, whereas a similar sample, which will hereinafter be described more fully, was kept extremely dehydrated prior to activation and found to require only 5.2% SiF4 to produce optimum cracking activity, and gave an exceptionally good yield of gasoline.

An important advantage of my invention is that the activating treatment can be carried out by depositing the dehydrated alumina compound as a stationary bed or mass in a hydrocarbon conversion zone and then merely passing a stream of anhydrous SiF4 through the mass at ordinary temperature and pressure. There are some advantages in employing a temperature of about 70 to 700 F. On the other hand, the treatment can be carried out under substantially the same conditions of temperature and pressure as prevail during the catalytic conversion reaction in which the activated catalyst is to be employed, namely, 700 to 950 F. I

Reactivation of used catalysts is also contemplated. Thus, in the case of a fixed catalyst bed type of operation for the cracking of gas oil wherein two or more contact masses are used, hydrocarbons undergoing conversion being passed through one mass while another mass is of!- stream undergoing regeneration, the fresh catalyst or freshly regenerated catalyst or mixtures of both may be treated in situ with SiF4. This reactivating treatment advantageously follows the regenerating treatment to remove carbonaceous material and precedes reintroduction of feed gas oil vapors to the cracking reaction.

In a fluidized catalyst system where the catalyst is used as a dry powder suspended in the gaseous reactants, the stream of powdered cat; alyst leaving the regenerating zone can be readily subjected to brief contact with a small amountof dry SiF4 for the-purpose of maintaining it at a uniformly high level of activity. Likewise, the catalyst in a moving bed type of operation can be continually treated and reactivated.

Accordingly, these reactivating treatments, with SiFl can be applied to the catalyst either with or without substantially reducing the temperature of the catalyst in the conversion system. A further advantage of the anhydrous gaseous activating and reactivating agent of my invention is that the treatment is applied to the catalyst without subjecting it to wetting, which is impossible without drastic reduction in temperature. This is particularly advantageous in a fluid catalyst system since wetting of the catalyst powder at any temperature interferes with a cracking temperature in the range 800 to 950 F. were passed throughv the catalyst mass at a space velocity of 2.0 volumes of gas oil measured as liquid at 60 F., per hour, per volume of catalyst. The flow of gas oil vapor through the mass was continued for 2 hours. The total hydrocarbon product obtained over the 2-hour period was fractionated to determine the yield a of gasoline having an end boiling point of about 400 F. as per cent by weight of gas oil feed.

Tests were conducted on the gasoline to establish its desirable character.

SiF4 was prepared by mixing 4 parts of calcium fluoride, 2.3 parts of sand, and 5 parts of concentrated sulfuric acid (98%+) together in a Pyrex glass flask and warming slightly to drive of! the SiF4 generated. The SiF4 was freed from HF by passing through silica gel in a drying tower.

Example 1 Dehydrated aluminum oxide, Alorco-A, in I granular form, 8-14 mesh, was placed in an electrically heated iron vessel and purged with a slow stream of carbon dioxide gas at a temperature of 860 F. for fifteen minutes. Heating was then discontinued, and dry SiF4 gas which contained about 15% dry air was passed into the vessel while slowly rotating to distribute the gas to the solid in a uniform manner. The aluminum oxide absorbed about 7.9% by weight of SiF4, and at the end of the activation, which required only a few minutes, the temperature had fallen to 680 F. The activated granular catalyst, which had retained its original physical form, was then placed in the cracking reactor, and gas-oil vapor was passed through the reactor at a temperature of 950 F. and under the previously stated conditions of space velocity (2.0) and time (2.0 hr.) thereby obtaining a gasoline yield of 26% by weight based on the gas-oil charge.

Example 2 Dehydrated aluminum oxide, Alorco-A, was placed in a Pyrex glass vessel and the vessel evacuated with a vacuum pump. Silicon tetrafiuoride which contained approximately 15% dry air was slowly admitted. The starting temperature under the foregoing conditions of space velocity and time, the gas-oil vapor was converted into gasoline to the extent of 26.5% by weight.

When the dehydrated alumina, Alorco-A, was used in the cracking reaction under the same conditions of space velocity and temperature and 7 using the same gas-oil vapor as in the case of Example 2, and without any activation with SiFi, only 4.1% of the gas-oil vapor was converted into gasoline.

Example 3 Dehydrated alumina, Alorco-A,'was placed in the reactor of th catalytic cracking apparatus, its temperature was adjusted to 950 F. and it was then purged with a slow stream of nitrogen for fifteen minutes. Gas-oil vapors preheated to 950 F. together with silicon tetrafluoride were then passed through the catalytic reactor. The space velocity of the gas-oil vapors was the same as that adopted as standard, and the rate of the SiF4 was approximately .014 cu. ft. per

Example 4 Dehydrated alumina, Alorco-A, was placed in a glass tube inch in diameter and 18 inches in length. The alumina was handled in moist air and no special precautions were taken to prevent the adsorption of some small amount of water vapor from the air. A mixture of 10% dry SiF4 and 90% dry nitrogen was passed through the fixed alumina bed at room temperature, (about 30 C.). Since the reaction generates some heat, the progress of the reaction could be followed through the bed by the advance of the heated zone. It is estimated that the temperature rose to 60 to 70 C. in the reaction zone. When the last layer had reacted, it was found that the alumina had absorbed 8.8% of SiF4, and

the activating time was 6 to 7 minutes. This ac-.

tivated alumina was then employed as a catalyst for cracking gas oil at 850 F. and under the foregoing conditions of space velocity and time, ohtaining a gasoline yield of 24.0%.

Example Aluminum oxide of the same character as used in the preceding example was soaked in acetic anhydride for a period of two weeks continu Example 6 A calcined alkali metal-free composite of precipitated silica, alumina and zirconia in the weight ratio of about 100 SiO2:2A.l2O3:5ZrO2, without treatment with SiF4 was employed as a cracking catalyst at a temperature of 850 F. under the foregoing conditions of space velocity and time, obtaining a gasoline yield of 25.2%.

Example 7 A sample of the same synthetic gel catalyst used in Example 6 was placed in the reactor of the catalytic cracking apparatus and the temperature adjusted to 850 F. The gas-oil vapors were then introduced into the reactor at the usual cracking rate mixed with SiF4 which was introduced at about .0071 cu. ft. per minute. At the end of 17 minutes the SiF4 was discontinued while the gas-oil vapor was continued over the catalyst for the usual two-hour period. The total SiF4 introduced amounted to 17.5% of the I weight of the catalyst although some of the gas passed through unreacted. The gasoline yield was 32.6%.

Example 8 A sample of granular Porocel was dried 3 hours.

at 500 F., placed under vacuum and cooled to room temperature, and reacted with S1F4 gas at room temperature whereby 4.63% was added to the weight of the alumina. When used as a catalyst to crack gas-oil at 850 F. and at the foregoing space velocity and for the usual two-hour period, a gasoline yield of 21.3% was obtained.

Example 9 A sample of granular Porocel, 4-10 mesh, thoroughly dried by heating 15 hours at 1000 F;, Was placed in the cracking reactor, and while passing gas-oil at the usual space velocity and at 850 F., SiF4 gas was also introduced with the oil vapors at about .0071 cu. ft. per minute for the first fourteen minutes of the cracking test, after which the SiF4 was discontinued and the oil vapor continued for the usual two-hour period. The SiF4 introduced was about 13.5% of the weight of the alumina although a small amount passed through the alumina unreacted near the end of the 14-minute activating period The gasoline yield was 22.1%.

Example 10 Example 11 Dehydrated alumina, Alorco-A, was placed in the reactor of the cracking apparatus and gasoil vapor passed through at the usual space velocity and at 900 F. Activation of the catalyst consisted of passing SiF4 gas along with the oil vapors for the first 15 minutes of the cracking test and until SiF4 amounting to 13.7% of the weight of the alumina had entered. The oil vapor was continued for the usual two-hour period.

. The gasoline yield was 28.6%.

Example 12 Dehydrated alumina, Alorco-A, was placed in the reactor of the cracking apparatus, and. gasoil vapor passed through at the usual space velocity and at 850 F. Activation of the catalyst consisted of passing SiF4 gas along with the oil vapors for the first 15 minutes of the cracking test and until SiF4 amounting to 14.3% of the weight of the alumina had entered. The oil vapor was continued for the usual two-hour period. The gasoline yield was 26.7

Example 13 A sample of Alorco-A which normally contains a little less than 1% of sodium oxide was washed repeatedly with 1.0% hydrochloric acid which was free of sodium salts. The sample was then washed repeatedly with distilled water to substantially lower the content of sodium. The sample was then dried at about, 100 C. and placed in an electrically heated tube where it was thoroughly dried with a slow stream of nitrogen at a temperature of 700 F. While still maintained at 700 F. a mixture of 31F; and 90% dry nitrogen (by volume) was slowly circulated through the alumina until the reaction stopped and it was found that 7.1% SiF4 had been absorbed. The alumina thus-activated was used in a cracking test in which the gas-oil was passed over the catalyst at the foregoing space velocity and at 850 F. for a two-hour period. The gasoline yield was 25.4%.

Example 14 A sample of Alorco-A was placed in an electrodialysis cell, where it was surrounded by distilled water and exposed to an electric field, so that sodiurn was rapidly driven out of the alumina granules. After 144 hours of continuous electrodialysi's, the sodium impurity of the alumina was reduced to a very small trace. Th granular form and physical properties of the alumina were retained. The sample was dried at 100 C. and then further dehydrated by heating to 550 F. for a period of 2.hours. The alumina was then cooled in an evacuated vessel, and SiFt gas admitted at room temperature until the alumina had gained 7.8% by weight by absorption of the fluoride gas, When used in the catalytic cracking of gas-oil under the foregoing conditions of space velocity and time and at 850 F., a gasoline yield of 26.7% was obtained.

In all of the foregoing examples the activated catalyst was found to have retained the granular form, and the good porosity and mechanical strength which is characteristic of the better grades of dehydrated alumina.

The results obtained in Exampl 5, when compared with other examples, indicate that a superior catalyst is obtained by treating the aluminum oxide in the absence of any adsorbed water, and also by the use of a smaller-amount of SiF4.

Examples 6 and '7 indicate that a synthetic gel type catalyst which contains alumina but has a high content of silica is improved in activity for cracking by treating with S1F4.

While the foregoing examples have to do with catalytic cracking of gas-oil, it is contemplated that the invention has application to the cracking of other hydrocarbon fractions. It has application to the treatment of gasoline and naph the to effect reforming actions. It also has application to crackin of normally gaseous hydrocarbons at elevated temperatures. In general, the catalyst of this invention may be used for hydrocarbon conversion reactions at temperatures ranging from about 500 to 1000 F,

It may be used for the high temperature treatment of oils derived from other sources such as fatty oils and oxygenated hydrocarbon compounds.

Mention has been made of the catalyst of this invention having an enlarged surface area. By enlarged surface area it is contemplated that the catalyst will have a surface area in excess of square meters and up to 400 square meters per gram of catalyst.

Obviously many modifications and variations of the invention as above set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

' I claim: I

1. A method of catalytically converting hydrocarbon oil into gasoline hydrocarbons that comprises contacting the hydrocarbon oil at a temperature within the range of about BOO-950 F. with a, catalyst comprising alumina which has first been subjected to dehydration of such extent that not more than about 7% of firmly bound water remains in the catalyst and then treated with anhydrous silicon tetrafiuoride to effect absorption of silicon tetrafiuoride by the catalyst in amounts of about 545% by weight of the catalyst.

2. A method of converting hydrocarbon oil into gasoline hydrocarbons in contact with a catalyst comprising alumina that comprises subjecting the alumina catalyst to dehydration of such extent that not more than about 7% by weight of firmly bound water remains in the catalyst, thereafter passing a stream of anhydrous silicon tetrafiuoride and hydrocarbon vapors in contact with the catalyst with resultant absorp-, tion of silicon tetrafiuoride by the catalyst, then discontinuing the flow of the silicon tetrafiuoride and continuing the passage of the hydrocarbon vapors at a temperature in the rangeof about 800-950 F. in contact with the catalyst activated by the silicon tetrafiuoride absorption to effect the desired conversion.

ALLEN D. GARRISON.

REFERENCES CITED The following references are of record in the file of this patent: 1

UNITED STATES PATENTS Number Name Date 2,336,165 Connolly Dec. '7, 1943 2,346,012 Danforth Apr. 4, 1944 2,194,186 Pier et a1. Mar. 19, 1940 2,206,021 Clunck July 2, 1940 2,310,317 Roberts Feb. 9, 1943 2,330,685 Connolly Sept. 28, 1943 2,348,599 Brown May 9, 1944 2,331,473 Hyman Oct. 12, 1943 2,311,713 Thomas et a1 Feb. 23, 1943 2,380,489 Bailie July 31, 1945 OTHER REFERENCES Mellor, Comprehensive Treatise on'Inorganic and Theoretical Chemistry, 1925, Longman, Green and Co., New York, vol. 6, page 939. (Copy in division 59.),

Certificate of Correction Patent No. 2,425,463. August 12, 1947.

. ALLEN D. GARRISON It is hereby certified that errors appear in'the printed specification of the above numbered patent requiring correction as follows: Column 8, lines 49 and 50, Example 10, for vaports read vapors; line 51, same Example for under read until; same line 51, for 123% read 12.3%; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case I in the Patent Oflice.

Signed and sealed this 21st day of October, A. D. 1947.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

